Occurrence and Transport of Tetracycline, Sulfonamide, Quinolone

Published: February 10, 2011

r 2011 American Chemical Society 1827 dx.doi.org/10.1021/es104009s | Environ. Sci. Technol. 2011, 45, 1827–1833

ARTICLE

pubs.acs.org/est

Occurrence and Transport of Tetracycline, Sulfonamide, Quinolone,and Macrolide Antibiotics in the Haihe River Basin, ChinaYi Luo,*,†,‡ Lin Xu,†,‡ Michal Rysz,§,‡ Yuqiu Wang,† Hao Zhang,† and Pedro J. J. Alvarez*,||

†College of Environmental Sciences and Engineering; Ministry of Education Key Laboratory of Pollution Processes and EnvironmentalCriteria/Tianjin Key Laboratory of Environmental Remediation and Pollution Control, Nankai University, Wei Jin Road 94, Tianjin300071, China§GSI Environmental Inc., 2211 Norfolk, Suite 1000, Houston, Texas 77098, United States

)Department of Civil and Environmental Engineering, Rice University, MS 519, 5100Main Street, Houston, Texas 77005, United States

bS Supporting Information

ABSTRACT: The occurrence and transport of 12 antibiotics(from the tetracycline, sulfonamide, quinolone, and macrolidefamilies) was studied in a 72-km stretch of the Haihe River,China, and in six of its tributaries. Aqueous and sedimentsamples were analyzed byHPLC-MS/MS. Sulfonamides weredetected at the highest concentrations (24-385 ng/L) andhighest frequencies (76-100%). Eight of the 12 antibioticslikely originated from veterinary applications in swine farmsand fishponds, and concentrations at these sources (0.12-47 μg/L) were 1-2 orders of magnitude higher than in theeffluent of local wastewater treatment plants. Sulfachloropyr-idazine (SCP) was detected in all swine farm and fishpondsamples (maximum concentration 47 μg/L), which suggests itspotential usefulness to indicate livestock source pollution in the Haihe River basin. Hydrological and chemical factors that mayinfluence antibiotic distribution in the Haihe River were considered by multiple regression analysis. River flow rate exerted the mostsignificant effect on the first-order attenuation coefficient (K) for sulfonamides, quinolones, and macrolides, with higher flow ratesresulting in higherK, probably due to dilution. For tetracyclines, sediment total organic matter and cation exchange capacity exerteda greater impact on K than flow rate, indicating that adsorption to sediments plays an important role in attenuating tetracyclinemigration. Overall, the predominance of sulfonamides in the Haihe River underscores the need to consider regulating theirveterinary use and improving the management and treatment of associated releases.

’ INTRODUCTION

China leads the world in antibiotic production capacity,1 withan annual production of about 210 000 t, of which 85% is utilizedin animal agriculture and medicine.2 A significant percentage ofthese antibiotics (25-75%) is excreted unaltered in feces andpersists in soil after land application,3 which represents a non-point source that increases the concentration of antibioticresidues in the environment. Antibiotics from domestic sourcesand pharmaceutical industries can also be transported in sewageto wastewater treatment plants (WWTPs),4-6 where they tendto resist biodegradation7,8 and are discharged to rivers as pointsources in WWTP effluents.9-12 Additional potential sources ofantibiotics draining to aquatic ecosystem include feces fromconfined animal feeding operations (CAFOs),11,13,14 which areoften used as fertilizer (manure), and drainage from aquacultureponds.15 The increased presence of antibiotics in the environ-ment raises concerns about their propensity to select for resistantbacteria and facilitate the establishment and amplification ofpathogenic reservoirs that threaten public health.16-18 Potential

contamination of drinking water supplies by such emergingpollutants is also of concern.19

The types and concentrations of antibiotics in the environ-ment vary among areas and countries, depending on antibioticconsumption and use patterns.20 In some industrialized coun-tries, WWTP effluents containing antibiotics used in humanmedicine are the major sources of antibiotics in the aquaticenvironment.21 Antibiotic occurrence in aquatic systems is alsoaffected by their chemical stability and partition characteristics.22

For example, sulfonamides exhibit high solubility and chemicalstability in water, whereas macrolides tend to be hydrolyzed orsorbed to soil and sediments;23 quinolones are susceptible tophotodegradation24 and are also adsorbed in sediments;25 andtetracyclines have a high affinity for soil organic matter throughcation bridging and cation exchange.26-28 To date, valuable

Received: November 30, 2010Accepted: January 24, 2011Revised: January 19, 2011

1828 dx.doi.org/10.1021/es104009s |Environ. Sci. Technol. 2011, 45, 1827–1833

Environmental Science & Technology ARTICLE

insight on the fate of specific antibiotics has been obtainedthrough laboratory studies. Yet the environmental factors thatdetermine the reach and attenuation patterns of antibiotics at theregional scale are not fully understood, and limited data exist onthe spatial and temporal variability of antibiotic occurrence in theenvironment, which underscores the need for complementaryregional studies.

The Haihe River basin (discharging into the Bohai Sea) is thelargest water system in northern China and drains an area of265 000 km2 that includes the fastest growing economic region ofChina as well as 120 000 km2 of farmland.29 There are numerousinputs of antibiotics from livestock and aquaculture waste to theHaihe River. In the vicinity of the city of Tianjin (approximately10 million inhabitants), animal husbandry and aquaculturecontribute 57% of the total agricultural gross domestic product,which is twice China’s national average of 30%.30 Inputs fromhuman sources via WWTPs (which serve 90% of Tinajin’spopulation) have also been shown to be important sources ofpharmaceutical compounds.31 Previous studies reported thedetection of oxytetracycline (OTC), tetracycline (TC), sulfadia-zine (SD), ciprofloxacin (CIP), sulfachloropyridazine (SCP),and sulfamethoxazole (SM2) at 0.3-173 mg/kg in livestockexcrement at CAFOs along the Haihe River.32 However, nocomprehensive regional study has been conducted to character-ize the frequency of occurrence, migration, and attenuation ofselected antibiotics in the Haihe River basin and the relativecontributions from agricultural drainages and wastewater treat-ment plant discharges.

This study characterizes the occurrence of tetracycline, sulf-onamide, quinolone, and macrolide residues in the Haihe River andits main tributaries and assesses their sources and environmentalfactors that influence their migration and attenuation. The structuresand chemical properties of 12 selected antibiotics are shown in the

Supporting Information (Table S1). To our knowledge, this is thefirst regional study to systematically characterize the distribution,migration, and attenuation of selected antibiotics in the Haihe Riverbasin under varying hydrological conditions in light of their physi-cochemical properties.

’MATERIALS AND METHODS

Sampling Sites and Sample Collection. Multiple samplingpoints were established to investigate the loading and potentialmigration of antibiotics from putative sources to the Haihe Rivertributaries and subsequently to the main stream (Figure 1). Theseinclude six sites on the tributaries representing potential sources(S1-S6), at least two sampling sites for each of six tributaries (T1a,T1b, T2a, T2b, and so on), and nine sites on theHaihe River (M1-M9). Sites M1-M3 are located in an urban area with highpopulation density. The effluents from two of several WWTPslocated in this area (S1 and S2) were also sampled (see Table S2 inthe Supporting Information for additional information on WWTPsthat discharge to Haihe River tributaries). Sites M4-M7 werelocated in agriculturally influenced areas (Jinnan and Dongli Dis-tricts), which included fishponds, feedlots, and dairies. Sites M8 andM9 are located near the mouth of the Haihe River at 8 and 1 km,respectively from the Bohai Sea. Tributary sampling included animalfeces storage lagoons at two swine farms (S3, S4), and two fishponds(S5, S6). Background antibiotic concentrations upstream of theputative pollution sources were very low, if detected, accounting foronly 0.01-2% of the concentrations measured downstream of thesources (i.e., 6-23 ng/L).Surface water and surficial sediment samples were collected in

triplicate during two synoptic sampling events, in August 2009(high-flow period, sitesM1-M9) andDecember 2009 (low-flowperiod, sites M1-M9 and S1-S6). Samples were collected into

Figure 1. Sampling locations in the main stream of the Haihe River (M), tributaries (T), and potential antibiotic sources (S). Two locations (Ta, Tb)were sampled downstream from pollution sources at each tributary. Sampling locations are numbered along the river flow direction.



sterile, aluminum-covered containers (to prevent photodegrada-tion of antibiotics) and stored at 4 �C during transport to thelaboratory, where water samples were stored at 4 �C andsediment samples were stored at -18 �C until sample pretreat-ment, which occurred within 24 h of the sample collection.Sample Pretreatment and Solid-Phase Extraction. Sample

pretreatment and solid-phase extraction of both water and sedimentsamples was carried out as described previously18 (see SupportingInformation for details). Briefly, in addition to using standardadditions for quantification (see Analytical Method Validationsection below), [trimethyl-13C3]caffeine (Cambridge IsotopeLaboratories) was added to water and sediment samples as surrogateto compensate for matrix effects during both water and sedimentpretreatment. Simatone (Sigma-Aldrich, Germany) was also usedas internal standard to enhance analytical precision. Although use ofmultiple internal standards and/or surrogates is preferred to enhancethe accuracy of analysis of multiple compounds with differentphysicochemical properties, unavailability of some labeled antibioticsand budget constraints precluded this approach. Because of suchconstraints, several recent studies similarly relied on the standardsaddition method plus a single internal standard to analyze multipleantibiotics.33-37

During pretreatment, water samples (500 mL) were spikedwith 1 mL of 0.5 mg/L [trimethyl-13C3]caffeine and filteredthrough 0.45 μm glass fiber filters, and the pH was adjusted to5 with citrate buffer (Tianjin University, China). Divalent cations(Ca2þ, Mg2þ, Cu2þ, and Mn2þ), which have affinity for tetra-cyclines and macrolides, were complexed by the addition of 0.2 gof disodium ethylenediaminetetraacetate (Na2EDTA) to mini-mize interference during LC-MS/MS analysis. Simatone (100μg/L) was also added prior to analysis. To avoid interferencefrom dissolved organic matter, samples were also pretreated withStrata strong anion exchanger (SAX) cartridges followed byextraction with Oasis hydrophilic-liphophilic balance (HLB),as detailed in the Supporting Information.[trimethyl-13C3]Caffeine (1 mL of 0.5 mg/L) was also added

to 5 g of lyophilized and ground sediment samples, which wereextracted with 30 mL of extraction buffer including 15 mL ofmethanol (Sigma-Aldrich, St. Louis, MO), 5 mL of 0.1 M Na2-EDTA, and 10mL of citrate buffer (pH 5). Simatone (100 μg/L)was then added to the extract. The mixture was vortexed for1 min at 2500 rpm and extracted by ultrasonication for 15 min.The solution was centrifuged for 5 min at 4000 rpm, and 25 mLof supernatant was collected into a flask. The procedure wasrepeated three times by extracting three different aliquots of theinitial sample and then combining the three supernatants for avolume of approximately 75 mL. The final supernatant mixturewas blended and diluted to 500 mL with pure water.High-Performance Liquid Chromatography-Tandem

Mass Spectrometry Analysis. HPLC-MS/MS analysis wasperformed as described previously18 (see Supporting Informationfor details, including Table S3). Briefly, the Intersil ODS-3 column(2.1 � 250 mm, 5 μm particle size; GL Sciences, Japan) wasmaintained at 40 �C, with injection volumes of 10 μL. Acetonitrile(phase A) and purified water with 0.3% formic acid (v/v) (phase B)were used as mobile phases at a total flow rate of 0.2 mL/min, withthe following gradient: the contribution fromAwas linearly increasedfrom 10% to 30% over 2 min and held constant for 4 min. Then Awas increased to 35%over 4min andmaintained there for 5min. Thecycle was completed by returning A to the initial percentage (10%)over 4 min and maintaining for 6 min until the next injection.

Analytical Method Validation. Recoveries of the 12 targetcompounds were determined for surface water and sediment bythe standards addition method. Samples were spiked withdifferent antibiotic concentrations (10, 50, 100, and 500 ng/L forsurfacewater; 1, 10, 50, and 500 ng/g for sediment). Each samplewasspiked with all 12 antibiotics, dissolved in a methanol stock solution,and analyzed in triplicate after extraction with 15 mL of methanol(Sigma-Aldrich, St. Louis, MO), 5 mL of 0.1 M Na2EDTA, and10 mL of citrate buffer (pH 5). The respective recoveries of sulfo-namides, quinolones, tetracyclines, and macrolides were 71-92%,60-82%, 65-87%, and 59-80% in water samples and 72-91%,51-74%, 58-69%, and 67-69% in sediment samples. Recoveries of[trimethyl-13C3]caffeine for both water and sediment samples were71-90% (Tables S4-1 and S4-2, Supporting Information).Limits of detection were determined as the lowest concentra-

tion resulting in a signal-to-noise ratio (S/N) g 3. Analyticalmethod validation for water and sediment samples is described inthe Supporting Information (Tables S4-1 and S4-2). Reproduci-bility of response [peak area relative standard deviation (RSD, %)]was calculated from triplicate injections for each of three samplesspiked at the same concentration. RSD values ranged from 0.5% to2.5% forwater samples and from0.5% to 5.0% for sediment samples.Hydrological and Chemical Characteristics. The river flow

rate and flow velocity were measured with a MGG/KL-DC flowmeter (Kai Feng Kai Liu Instrument Co., Ltd.). Dissolvedorganic carbon (DOC) in the water column and total organiccarbon (TOC) in the sediments were measured with a ShimadzuTOC5000 analyzer. Cation-exchange capacity (CEC) was mea-sured by previously described methods.38

Antibiotics Attenuation Model. Antibiotics attenuation (e.g.,by adsorption, dilution, photolysis, hydrolysis, and biodegradation)was assumed (and confirmed) to follow first-order kinetics. Theattenuation coefficient (K) was calculated as39

K ¼ vL

� �ln

cicI

� �ð1Þ

where L is the distance from site i to site I; ci and cI are the antibioticconcentrations at sites i and I, respectively; and v is the average rivervelocity between the two sites.Kwas determined without the use ofconservative tracers thatwould be needed to quantify dilution. Thus,

Table 1. Average Antibiotic Concentrations in the WaterColumn Mainstream of the Haihe River

avg concn (ng/L)

antibiotica August 2009 December 2009

TMP (1.0 ( 0.7) � 102 (1.4 ( 0.8) � 102

SD (1.4 ( 0.8) � 102 (1.7 ( 0.8) � 102

SMZ (1.5 ( 0.9) � 102 (1.9 ( 1.0) � 102

SCP (1.6 ( 1.2) � 102 (2.1 ( 1.7) � 102

CIP (1.1 ( 0.8) � 102 (1.3 ( 0.5) � 102

VFX (1.7 ( 0.5) � 102 (1.8 ( 1.2) � 102

TC (2.6 ( 0.3) � 101 (2.7 ( 0.3) � 101

OTC (4.1 ( 0.2) � 101 (4.0 ( 0.0) � 101

ERY (3.4 ( 1.1) � 101 (3.8 ( 0.6) � 101

ROX (2.7 ( 1.4) � 101 (3.7 ( 0.8) � 101

aTMP = trimethoprim, SD = sulfadiazine,SMZ = sulfamethoxazole,SCP = sulfachloropyridazine, CIP = ciprofloxacin, VFX = ofloxacin,TC = tetracycline, OTC = oxytetracycline, ERY = erythromycin, andROX = roxithromycin.



K values represent overall attenuation coefficients that provideinsight on the relative persistence and potential reach of differentantibiotics (rather than specific degradation coefficients for use inpredictive fate and transport models).The first-order attenuation assumption was tested by assessing

the goodness of fit of the data to the exponential decay model [C =C0e

-KL/v] as described in the Supporting Information (Table S7).This model was only applied to segments with a single pollutionsource, usually located in the tributaries.Statistical Analysis. Antibiotic transport and attenuation in

aqueous systems can be influenced by their physicochemicalproperties as well as hydrological (flow rate) and chemical factorssuch as pH, dissolved organic matter (DOM) in the watercolumn, total organic matter (TOM) in sediments, and cation-exchange capacity (CEC) in sediments. These factors, whichaffectK, were measured (Table S7, Supporting Information) and

analyzed by multiple regression analysis using SPSS software.The standardized coefficient (β), which reflects the number ofstandard deviations the dependent variable increases or de-creases with one standard deviation increase in the independentvariable, was used to evaluate the influence of these factors on Kfor each of the 12 antibiotics at each of the six tributaries. A higherβ value indicates more significant influence of a given factor ontheK value. Negative β values indicate hydrological and chemicalfactors that hinder antibiotic attenuation. Significance wasassessed at the 95% confidence level (p < 0.05).

’RESULTS AND DISCUSSION

Antibiotics Occurrence in the Haihe River. Ten of the 12antibiotics targeted were detected in surface water samples of themain Haihe River during both sampling events [sulfamethazine

Figure 2. Spatial distribution of 12 antibiotics in the Haihe River main stream (August 2009). Colors reflect the four different classes of antibiotics:sulfonamides (pink), tetracyclines (green), macrolides (red), and quinolones (blue).

Figure 3. Relative antibiotic concentrations (normalized to correspondingpollution source concentrations) in Haihe River tributaries and the mainstream inDecember 2009. Significantly higher concentrationswere observedat the pollution sources, followed by concentrations in tributaries and in themain stream (p < 0.05). Error bars represent (1 standard deviation.

Figure 4. Attenuation coefficients and pseudopartitioning coefficients (P-PC) for antibiotics detected in the Haihe River basin. Results representaverage values ((1 standard deviation) for six tributary segments that weresampled in December 2009 (Table S7, Supporting Information).



(SM2) and enrofloxacin (ENR) were not detected] (Table S6,Supporting Information). Sulfonamides were the predominantantibiotics, detected with the highest frequencies (83-94%) andat the highest concentrations (210-385 ng/L). Relatively highconcentrations of SCP (176( 118 ng/L with a peak concentra-tion of 385 ng/L) were detected in M4-M7, where many swinefarms, dairies, and fishponds are located. SCP is used only as aveterinary antibiotic in the Haihe area, suggesting its potentialusefulness as a chemical marker for livestock source pollutionin the Haihe River basin, an application similarly suggestedfor sulfamethazine in the Mekong Delta, Vietnam.40 However,caution should be exercised about such inferences because SCPmay also be discharged from veterinary industries and wasdetected (though at significantly lower concentrations) at urbansitesM1-M3 and in wastewater treatment plant effluents (TableS6, Supporting Information).Temporal and Spatial Distribution of Antibiotics in the

Haihe River. Antibiotic concentrations in surface water weresignificantly higher (p < 0.01) during the winter season, exceptfor TC and OTC (Table 1). Lower detected antibiotic concen-trations in the summer can be attributed to higher runoff(increased flow rate), faster photolysis,23,41 thermal degradation(summer water temperature was approximately 26 �C versus5 �C in winter), and biodegradation associated with highermicrobial activity during the summer season.42-44

Eight of the 12 targeted pharmaceutical compounds weredetected at sites M1-M3 (urban areas with an approximatepopulation of 3.8 million). CIP and ofloxacin (VFX), which areused in human applications, were detected with highest frequen-cies (67% to 100%) at urban locations M1-M3. In contrast, theveterinary antibiotics sulfamethoxazole (SMZ), SCP, and SDwere detected with the highest frequencies (100%) at rural sitesM4-M7, which are located in the vicinity of numerous animal

husbandry and aquaculture industry operations, including ap-proximately 177 CAFOs and 66.7 km2 of aquaculture farms thatare often adjacent to the banks of the Haihe River. Significantconcentrations of antibiotics were detected in river sedimentscompared to the directly overlying water column samples(Figure 2), indicating the importance of sorption as an attenua-tion mechanism and underscoring the significance of sedimentsas antibiotic reservoirs in aquatic environments.Potential Sources of Antibiotics in the Haihe River. Anti-

biotic concentrations were analyzed in WWTP effluents, swinefarm lagoons, and fishponds that discharge to tributaries ofthe Haihe River. Eight veterinary pharmaceuticals belonging tothe tetracycline, sulfonamide, quinolone, and macrolide classeswere detected in swine farms and fishponds at 0.12-47 μg/L(Table S6, Supporting Information). These concentrations are 1-2orders of magnitude higher than those found in WWTP effluents,indicating significant contribution of veterinary pharmaceuticals tototal antibiotic residues in this region. The observed decrease inantibiotic concentrations (normalized to average pollution sourceconcentrations) along the flow direction from the putative source tothe tributaries to themain stream (Figure 3) support the hypothesisthat the antibiotics detected in the main stream originated frompotential agricultural sources along the tributaries. The averageconcentration of each antibiotic at these sources was 1-2 orders ofmagnitude higher than that in the main river.Antibiotic Attenuation. First-order attenuation rate coeffi-

cients (K values) for individual antibiotics were determined sepa-rately for each of six tributaries (Table S7, Supporting Informa-tion). The individual K values, averaged for the sampled segments(Figure 4), indicate that tetracyclines (K ranged from 0.39 to1.22 h-1) were most prone to attenuation, followed by macrolides(K ranged from 0.09 to 0.48 h-1), quinilones (K ranged from 0.08to 0.45 h-1), and sulfonamides (K ranged from 0.01 to 0.44 h-1).

Table 2. Multiple Regression Analysis (SPSS) of Hydrological and Chemical Factors Influencing Antibiotic AttenuationCoefficients (K)a

flow rate

(11.0-53.0 m3/s)

water pH

(6.2-7.6)

water DOC

(2.5-4.8 mg/L)

sediment TOC

(15.5-38.1 mg/g)

sediment CEC

(165-338 mmol/kg)

antibioticb Nc β pd β pd β pd β pd β pd

Sulfonamides

TMP 12 0.68 <0.01 0.14 0.10 -0.37 0.03 -0.04 0.62 -0.06 0.53

SMZ 18 0.56 0.01 0.05 0.63 -0.47 0.02 -0.08 0.60 0.00 0.96

SD 12 0.59 0.03 0.24 0.08 -0.41 0.04 -0.05 0.70 -0.41 0.78

SCP 18 0.54 <0.01 0.06 0.50 -0.45 0.01 0.02 0.80 0.00 0.90

Quinolones

CIP 12 0.70 <0.01 0.07 0.25 -0.35 0.01 -0.10 0.27 0.00 0.96

VFX 12 0.48 0.05 0.19 0.18 -0.45 0.07 -0.11 0.58 -0.17 0.36

Macrolides

ERY 12 0.58 0.05 0.16 0.29 -0.42 0.12 -0.03 0.89 -0.11 0.59

ROX 18 0.57 0.03 -0.02 0.89 -0.42 0.07 -0.14 0.45 -0.01 0.97

Tetracyclines

OTC 18 0.05 0.74 0.24 0.04 -0.10 0.50 0.54 <0.01 0.42 0.01

TC 12 0.20 0.40 0.19 0.20 0.26 0.30 0.51 0.05 0.48 0.04aMeasured ranges of hydrological and chemical factors are shown in parentheses. bTMP = trimethoprim, SMZ = sulfamethoxazole, SD = sulfadiazine,SCP = sulfachloropyridazine, CIP = ciprofloxacin, VFX = ofloxacin, ERY = erythromycin, ROX = roxithromycin, OTC = oxytetracycline, and TC =tetracycline. c N represent number of samples analyzed. d Significance of the effect of hydrological and chemical factors on K was assessed at the 95%confidence level (p < 0.05) and is indicated by boldface type.



Sorption to sediments is an importantmechanism contributing tothe relatively high attenuation capacity for tetracyclines and macro-lides, as suggested by previous lab studies.28,4546 Although antibioticpartitioning betweenwater and river sediments is a dynamic process,the relative importance of sorption as an attenuation mechanism canbe assessed by normalizing antibiotic concentrations in the watercolumn by the corresponding concentrations in directly underlyingsediments, to estimate pseudopartitioning coefficients (P-PC, litersper kilogram) (Figure 4). P-PC values were highest for tetracyclines(1410L/kg forTC, 1398L/kg forOTC),which likely contributed tothe relatively low aqueous tetracycline concentrations (Figure 2).The significance of sorption for the relatively fast attenuation oftetracyclines (Figure 4) is also inferred by the highβ values associatedwith sedimentTOCandCEC (Table 2), which respectively facilitatesorption through cation bridging and cation exchange.26-28

The river flow rate exerted the most significant effect on theoverall K values for sulfonamides, quinolones, and macrolides(Table 2), indicating that dilution plays an important role in theattenuation of these three antibiotic classes. Slower attenuation ofmacrolides, quinolones, and sulfonamides was significantly corre-lated with higher DOC (negative β values). Apparently, somefunctional groups in dissolved organic matter (e.g., carboxyl, hydro-xyl, carbonyl) facilitate electrostatic association with these antibioticsand enhance theirmigration by cotransport, as previously reported.47

Overall, this work shows a predominant presence of sulfona-mides in the Haihe River basin, which are discharged to itstributaries from swine farm lagoons and fishponds. This under-scores the need to consider more efficient practices for manage-ment of livestock waste and aquaculture drainage and theirtreatment prior to reuse or discharge. Given the persistenceand high migration propensity of sulfonamides, further researchis also needed to better understand their fate in the environment,their impact on the establishment and amplification of antibioticresistance reservoirs, and the associated risks to public health.

’ASSOCIATED CONTENT

bS Supporting Information. Additional text and seven ta-bles describing structure and physicochemical properties of the12 antibiotics investigated in this study, information on waste-water treatment plants in Tianjin, details on sample extractionand pretreatment, antibiotic concentration data at differentsampling locations and times, analytical methods validation,determination of first-order attenuation rate coefficients, anddata for hydrological and chemical variables that may influenceantibiotic distribution. This material is available free of charge viathe Internet at http://pubs.acs.org.

’AUTHOR INFORMATION

Corresponding Author*Tel þ86 (22) 23508535, e-mail [email protected] (Y.L.);tel (713) 348-5903, e-mail [email protected] (P.J.J.A.).

Author Contributions‡Y.L., L.X., and M.R. contributed equally to this work.

’ACKNOWLEDGMENT

This work was supported by the National Nature Science Foun-dation of China (Grants 20777041, 30870363, and 31070333) andTianjin Nature Science Foundation (Grant 08JCYBJC02700).

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Occurrence and Transport of Tetracycline, Sulfonamide, Quinolone